EP2325291B1 - Olefin Copolymer VI improvers and lubricant compositions and uses thereof - Google Patents

Olefin Copolymer VI improvers and lubricant compositions and uses thereof Download PDF

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Publication number
EP2325291B1
EP2325291B1 EP10188282A EP10188282A EP2325291B1 EP 2325291 B1 EP2325291 B1 EP 2325291B1 EP 10188282 A EP10188282 A EP 10188282A EP 10188282 A EP10188282 A EP 10188282A EP 2325291 B1 EP2325291 B1 EP 2325291B1
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Prior art keywords
olefin copolymer
copolymer
lubricating oil
olefin
oil
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EP10188282A
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German (de)
English (en)
French (fr)
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EP2325291A1 (en
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Akhilesh Duggal
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Afton Chemical Corp
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Afton Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/005—Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
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    • C10N2010/12—Groups 6 or 16
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/68—Shear stability
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Definitions

  • the viscosity of lubricating oils is typically dependent on temperature. With an increase in oil temperature, the viscosity of the oil generally decreases; as the temperature of the oil decreases, the viscosity of the oil generally increases. At high temperatures where modem engines typically operate, it is important to maintain viscosity within specified ranges to properly lubricate moving parts of the engine. Additionally, the lubricating oils may be exposed to low temperatures from the environment when the engines are shut off; in these conditions, the viscosity of the oil must be low enough so that the oil will flow when under engine starting conditions. The acceptable oil viscosity ranges for high and low temperatures are specified by the SAE J300 standard.
  • Viscosity index improvers reduce the extent to which the viscosity of lubricants change with temperature, and are used to formulate oils that meet the SAE J300 standard.
  • Suitable Viscosity Index Improvers are polymeric materials that may be derived from ethylene-proplyene copolymers, polymethacrylates, hydrogenated styrene-butadiene copolymers, polyisobutylenes, etc.
  • the high ethylene polymers e.g., ethylene contents of 65 mole% to 85 mole% ethylene, are used to improve low temperature properties of lubricating oils.
  • ethylene contents e.g., 65 mole% to 85 mole% ethylene
  • polymers with high ethylene content are thought to undergo intramolecular contraction or folding, leading to a lower viscosity of the oil, when compared to a low ethylene ( ⁇ 60 mole%) amorphous polymers that do not exhibit such behavior.
  • low temperature properties such as CCS (cold crank simulator) Birdiviscosity
  • a high ethylene polymer chain may also interact with other chains, or with waxy components that are contained in the oil composition, leading to gel formation.
  • Gel formation is undesirable, as it causes a lack of lubricating oil circulating to the engine, which may lead to engine failures.
  • high levels of pour point depressant may be added to the oil. Higher levels of pour point depressants serve to mitigate but not completely solve the problem.
  • the disclosure provides a lubricating oil composition and methods of operating an internal combustion engine to provide improved engine operational performance.
  • the lubricating composition includes a major amount of oil of lubricating viscosity; a minor amount of at least one olefin copolymer having a number average molecular weight greater than 10,000 up to 300,000.
  • the lubricating oil composition may optionally include a minor amount of at least one non-grafted olefin copolymer, styrene-isoprene copolymer, methacrylate copolymer, or styrene butadiene copolymer have number average molecular weight greater than 50,000 up to 300,000.
  • the lubricating oil composition may optionally include a minor amount of at least one non-grafted olefin copolymer, styrene-isoprene copolymer, methacrylate copolymer, or styrene butadiene copolymer have number average molecular weight greater than 50,000 up to 300,000.
  • the disclosure is directed to improved grafted olefin copolymer viscosity index improvers (VII's) having improved high and low temperature properties.
  • VI's grafted olefin copolymer viscosity index improvers
  • the olefin copolymer VII's described herein may be used in a variety of applications including, but not limited to, engine lubrication, transmission oils, and industrial oils.
  • a primary substrate for making the VII's described herein is a copolymer is derived from ethylene monomer and one or more C 3 to C 23 alpha-olefin monomers. Copolymers of ethylene and propylene are suitably used to make the copolymer.
  • Copolymers herein may include without limitation blends or reacted products of ethylene and one or more C 3 to C 23 alpha-olefins. The copolymers may optionally include dienes or polyenes. Thus, the terms “polymers” and “copolymers”, as used herein may also include terpolymers, and other higher polymer forms.
  • polymer and “copolymer” are used generically to encompass ethylene copolymers, terpolymers or interpolymers. Such materials may contain amounts of other olefinic monomers so long as the basic characteristics of the polymers are not materially changed.
  • copolymer substrate Methods for making the copolymer substrate described above are described, e.g., in U.S. Pat. Nos. 4,863,623 , 5,075,383 , and 6,107,257 .
  • the polymer substrate also may be commercially obtained having the properties indicated herein.
  • More complex polymer substrates also may be used as the olefin polymer starting material, which may be prepared using a third component.
  • the third component generally used to prepare an interpolymer substrate is a polyene monomer selected from nonconjugated dienes and trienes.
  • The-non-conjugated diene component is one having from 5 to 14 carbon atoms in the chain.
  • the diene monomer may be characterized by the presence of a vinyl group in its structure and can include cyclic and bicyclo compounds.
  • dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylnorbornene, 5-methylene-2-norborene, 1,5-heptadiene, and 1,6-octadiene.
  • a mixture of more than one diene may be used in the preparation of the interpolymer.
  • a suitable nonconjugated diene for preparing a terpolymer or interpolymer substrate is 1,4-hexadiene.
  • the triene component may have at least two nonconjugated double bonds, and up to about 30 carbon atoms in the chain.
  • Typical trienes that may be used to prepare the interpolymer are 1-isopropylidene-3 ⁇ ,4,7,7 ⁇ -tetrahydroindene, 1-isopropylidene-dicyclopentadiene, dihydro-isodicyclopentadiene, and 2-(2-methylene-4methyl-3 -pentenyl)[2.2.1 ]bicyclo-5-heptene.
  • Ethylene-propylene or higher alpha-olefin copolymers may consist of from 15 to 85 mole percent ethylene and from 85 to 15 mole percent C 3 to C 23 alpha-olefin with the mole ratios in one embodiment being from 40 to 70 mole percent ethylene and from 60 to 30 mole percent of a C 3 to C 23 alpha-olefin, with the proportions in another embodiment being from 60 to 85 mole percent ethylene and 40 to 15 mole percent C 3 to C 23 alpha-olefin, and the proportions in yet another embodiment being from 55 to 65 mole percent ethylene and 45 to 35 mole percent C 3 to C 23 alpha-olefin.
  • Terpolymer variations of the foregoing polymers may contain from 0 to 10 mole percent of a nonconjugated diene or triene. Other termonomer levels are less than 1 mole percent.
  • a particularly suitable copolymer substrate is a substantially linear copolymer of ethylene and propylene having an ethylene content ranging from 60 to 85 percent by weight and having a number average molecular weight from 10,000 to 300,000, and for example a number average molecular weight of 100,000 to 200,000, as determined by gel permeation chromatography utilizing polystyrene standards.
  • the polymer described above i.e., the olefin copolymer substrate, may be conveniently obtained in the form of ground or pelletized polymer.
  • the olefin copolymer may also be supplied as either a pre-mixed bale or a pre-mixed friable chopped agglomerate form.
  • ground polymer bales or other forms of the olefin copolymer are fed to an extruder, e.g., a single or twin screw extruder, or a Banbury or other mixer having the capability of heating and effecting the desired level of mechanical work (agitation) on the polymer substrate for the dehydration step.
  • a nitrogen blanket can be maintained at the feed section of the extruder to minimize the introduction of air.
  • the olefin copolymer may initially be heated before being admixed with any other reactants in the extruder or other mixer with venting to eliminate moisture content in the feed material.
  • the dried olefin copolymer is in one embodiment then fed into another extruder section or separate extruder in series for conducting the grafting reaction.
  • Suitable graft components may be selected from vinyl aromatic compounds, C 5 -C 30 olefins, and polyalkylene.
  • Suitable vinyl aromatic compounds are those corresponding to the following formula wherein R 1 and R 2 , independently from each other, represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • styrene o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, m-isopropylstyrene, p-isopropylstyrene, alpha-methylstyrene, o-methyl-alpha-methylstyrene, m-methyl-alpha-methylstyrene, p-methyl-alpha-methylstyrene, m-isopropyl-alpha-methylstyrene, and p-isopropyl-alpha-methylstyrene.
  • the olefin compounds that may be used are primarily C 5 -C 30 linear or branched olefins having internal or terminal unsaturation.
  • a particularly suitable olefin component to be grafted to the copolymer backbone is a substantially linear, alpha olefin having at least about 90 mole percent terminal olefins comprised of at least 95 mole percent of C 10 -C 18 olefins.
  • the polyalkylene component may be selected from polybutenes and highly reactive polybutenes having a number average molecular weight ranging from about 400 to about 3000 or more.
  • the term "highly reactive" means that a number of residual vinylidene double bonds in the compound is greater than about 45%.
  • the number of residual vinylidene double bonds may range from about 50 to about 85 % in the compound.
  • the percentage of residual vinylidene double bonds in the compound may be determined by well-known methods, such as for example InfraRed Spectroscopy or C13 Nuclear Magnetic Resonance or a combination thereof. A process for producing such compounds is described, for example, in U.S. Patent No. 4,152,499 .
  • a particularly suitable compound is a polyisobutene having a ratio of weight average molecular weight to number average molecular weight ranging from about 1 to about 6 and a number average molecular weight ranging from about 500 to about 1500.
  • the mixture of grafting components includes at least one component selected from (A) vinyl aromatic compounds and at least one component selected from (B) olefins and/or polyakylene compounds wherein a mole ratio of A/B in the mixture ranges from 0.25:1 to 5.0:1, for example, from 0.5:1 to 2.5:1, more suitably from 0.75:1 to 1.5:1.
  • the amount of grafting components e.g., vinyl aromatic compound, olefin and/or polyisoalkylene
  • the copolymer may include from 1 wt% to 30 wt% of the grafting components.
  • the grafting reaction to form the grafted olefin copolymers is generally carried out with the aid of a free-radical initiator in bulk in an extruder in the substantial absence of solvent.
  • the free-radical initiators which may be used to graft the component to the polymer backbone include peroxides, hydroperoxides, peresters, and also azo compounds and preferably those which decompose thermally within the grafting temperature range to provide free radicals.
  • azobutyronitrile dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.
  • the initiator may be used in an amount ranging from about 0.005% to about 2% by weight based on the weight of the reaction mixture, desirably from about 0.2% to about 1% by weight.
  • the graft component, olefin copolymer, and initiator are in one embodiment fed to an extruder, e.g., a single or twin screw extruder or other mixer, having the capability of heating and effecting the desired level of mechanical work (agitation) on the reactants for the grafting step.
  • the initiator may be added as a solution in the grafting components or an inert solvent, such as but not limited to mineral oil.
  • grafting is conducted in an extruder, and particularly a twin screw extruder. A nitrogen blanket is maintained at the feed section of the extruder to minimize the introduction of air.
  • the extruder is equipped with a vent to facilitate removal of unreacted grafting components and by-products of the grafting reaction.
  • the grafting components may be injected at one injection point, or is alternatively injected at two injection points in a zone of the extruder without significant mixing e.g. a transport zone. Such injection may result in an improved efficiency of the grafting and may lead to a lower gel content of the grafted copolymer.
  • Suitable extruders are generally known available for conducting grafting, and the prior dehydration procedure.
  • the dehydration of the polymer substrate and subsequent grafting procedures may be performed in separate extruders set up in series.
  • a single extruder having multiple treatment or reaction zones may be used to sequentially conduct the separate operations within one piece of equipment. Illustrations of suitable extruders are set forth, e.g., in U.S. Pat. No. 3,862,265 and U.S. Pat. No. 5,837,773 .
  • the olefin copolymer In forming the grafted olefin copolymers, the olefin copolymer generally is fed to plastic processing equipment such as an extruder, intensive mixer or masticator, heated to a temperature of at least 60°, for example, 150° to 240° C., and the grafting components and free-radical initiator are separately fed to the molten copolymer to effect grafting. In another embodiment, all three of the grafting components, copolymer and initiator may be fed to the extruder at substantially the same time. The reaction is carried out optionally with mixing conditions sufficient to effect grafting of the olefin copolymers.
  • the processing equipment is generally purged with nitrogen to prevent oxidation of the copolymer.
  • the processing equipment is equipped with a vent in order to facilitate removal of unreacted reagents and byproducts of the grafting reaction.
  • the residence time in the processing equipment is controlled to provide for the desired degree of grafting and to allow for purification of the grafted copolymer via venting.
  • Mineral or synthetic lubricating oil may optionally be added to the processing equipment after the venting stage to dissolve the grafted copolymer.
  • the grafted copolymer exits from the die face of the extruder either immediately after grafting, or after shearing and vacuum stripping (discussed below in more detail) if performed in different sections of the same extruder or a separate extruder arranged in series with the extruder in which grafting is conducted.
  • the grafting reaction may also be carried out in the presence of a hydrocarbon solvent.
  • Hydrocarbon solvents that may be used include open-chain aliphatic compounds such as C 9 or lower alkanes, alkenes and alkynes (e.g., C 5 to C 8 alkanes such as hexane); aromatic hydrocarbons (e.g., compounds having a benzene nucleus such as benzene and toluene); alicyclic hydrocarbons such as saturated cyclic hydrocarbons (e.g., cyclohexane); ketones; or any combinations of these.
  • Solvent grafting may be conducted in a pressurized (above atmospheric pressure) reactor or a series of pressurized reactors.
  • the molecular weight of the grafted olefin copolymer may be reduced by mechanical, thermal, or chemical means, or a combination thereof. Techniques for degrading or reducing the molecular weight of such copolymers are generally known in the art. The number average molecular weight is reduced to suitable level for use in single grade or multigrade lubricating oils.
  • the grafted copolymer has an initial number average molecular weight ranging from about 10,000 to about 500,000 upon completion of the grafting reaction. In one embodiment, to prepare an additive intended for use in multigrade oils, the copolymer's number average molecular weight is reduced down to a range of about 100,000 to about 200,000 as measured by gel permeation chromatography using polystyrene calibration standards.
  • grafting and reduction of the high molecular weight olefin copolymer may be done simultaneously.
  • the high molecular weight olefin copolymer may be first reduced to the prescribed molecular weight before grafting.
  • the olefin copolymer's average molecular weight is reduced before grafting, its number average molecular weight is sufficiently reduced to a value below about 250,000, e.g., in the range of about 100,000 to 200,000.
  • Reduction of the molecular weight of the olefin copolymer feed material during or prior to grafting, to a prescribed lower molecular weight typically is conducted in the absence of a solvent or in the presence of a base oil, using either mechanical, thermal, or chemical means, or combination of these means.
  • the olefin copolymer is heated to a molten condition at a temperature in the range of about 200° C. to about 350° C. and it is then subjected to mechanical shear, thermally or chemical induced cleavage or combination of said means, until the copolymer intermediate (or olefin copolymer) is reduced to the prescribed molecular weight.
  • the shearing may be effected within an extruder section, such as described, e.g., in U.S. Pat. No. 5,837,773 .
  • mechanical shearing may be conducted by forcing the molten copolymer through fine orifices under pressure or by other mechanical means.
  • grafting components and free radical initiator usually are removed and separated from the grafted copolymer product.
  • the unreacted components may be eliminated from the reaction mass by vacuum stripping, e.g., the reaction mass may be heated to temperature of about 150° C. to about 450° C. under agitation with a vacuum applied for a period sufficient to remove the volatile unreacted grafting component and free radical initiator ingredients.
  • Vacuum stripping may be performed in an extruder section equipped with venting means.
  • the grafted copolymer may be formed into pellets by a variety of process methods commonly practiced in the art of plastics processing. Such techniques include underwater pelletization, ribbon or strand pelletization or conveyor belt cooling. When the strength of the copolymer is inadequate to form into strands, the preferred method is underwater pelletization. Temperatures during pelletization should not exceed 30° C. Optionally, a surfactant may be added to the cooling water during pelletization to prevent pellet agglomeration.
  • the mixture of water and quenched copolymer pellets is conveyed to a dryer such as a centrifugal drier for removal of water.
  • Pellets may be collected in a box or plastic bag at any volume for storage and shipment. Under some conditions of storage and/or shipment at ambient conditions, pellets may tend to agglomerate and stick together.
  • the pellets may be ground by mechanical methods to provide high surface area solid pieces for easy and quick dissolution into oil.
  • the grafted olefin copolymers of the present disclosure may be incorporated into lubricating oil in any convenient way.
  • the grafted olefin copolymers may be added directly to the lubricating oil by dispersing or dissolving the same in the lubricating oil at the desired level of concentration. Such blending into the lubricating oil may occur at room temperature or elevated temperatures.
  • the grafted olefin copolymers may be blended with a suitable solvent/diluent (such as, lubricating base oils and petroleum distillates) to form a concentrate, and then blending the concentrate with a lubricating oil to obtain the final formulation.
  • a suitable solvent/diluent such as, lubricating base oils and petroleum distillates
  • Such additive concentrates will typically contain (on an active ingredient (A.I.) basis) from about 3 to about 25 wt. %, for example, from about 5 to about 15 wt. %, grafted olefin copolymer additive, and typically from about 75 to 97 wt %, and suitably from about 85 to 95 wt %, base oil based on the concentrate weight.
  • active ingredient A.I.
  • grafted olefin copolymer additive typically from about 75 to 97 wt %, and suitably from about 85 to 95 wt %, base oil based on the concentrate weight.
  • Lubricating oil formulations for internal combustion engines as described herein may conventionally contain additional additives that will supply the characteristics that are required in the formulations.
  • additional viscosity index improvers include antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, antifoaming agents, demulsifiers and friction modifiers.
  • DI dispersant/inhibitor
  • One component of the DI package is a metal-containing or ash-forming detergent that functions as both a detergent to reduce or remove deposits and as an acid neutralizer or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450.
  • Combinations of detergents, whether overbased or neutral or both, may be used.
  • In one preferred lubricating oil composition In one preferred lubricating oil composition.
  • Detergents generally useful in the formulation of lubricating oil compositions also include "hybrid" detergents formed with mixed surfactant systems, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos. 6,153,565 , 6,281,179 , 6,429,178 and 6,429,179 .
  • Dispersants maintain in suspension materials resulting from oxidation during use that are insoluble in oil, thus preventing sludge flocculation and precipitation, or deposition on metal parts.
  • Dispersants useful in the context of the disclosure include the range of nitrogen-containing, ashless (metal-free) dispersants known to be effective to reduce formation of deposits upon use in gasoline and diesel engines, when added to lubricating oils.
  • Mannich base condensation products Another class of high molecular weight ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing about one mole of a long chain alkyl-substituted mono- or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Pat. No. 3,442,808 .
  • carbonyl compound(s) e.g., formaldehyde and paraformaldehyde
  • Such Mannich base condensation products may include a polymer product of a metallocene catalyzed polymerization as a substituent on the benzene group, or may be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Pat. No. 3,442,808 .
  • Other suitable dispersants are described in U.S. Pat. Nos.
  • additives may be incorporated into the compositions of the disclosure to enable particular performance requirements to be met.
  • additives which may be included in the lubricating oil compositions of the present disclosure are metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, anti-foaming agents, anti-wear agents and pour point depressants. Some are discussed in further detail below.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition.
  • Particularly desirable zinc salt include zinc dihydrocarbyl dithiophosphates thatmay be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
  • Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons or esters, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Pat. No. 4,867,890 , and molybdenum-containing compounds.
  • Aromatic amines having at least two aromatic groups attached directly to the nitrogen constitute another class of compounds that is frequently used for antioxidancy. While these materials may be used in small amounts, preferred embodiments of the present disclosure are free of these compounds.
  • the amount of aromatic amines may range from about 0.1 to about 1.5 percent by weight of the total weight of the lubricating oil composition.
  • a particularly useful amount of aromatic amines may be from about 0.4 wt. % or more based on the total weight of the lubricating oil composition.
  • suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene.
  • Friction modifiers and fuel economy agents that are compatible with the other ingredients of the final oil may also be included.
  • examples of such materials include glyceryl mono- and di-esters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; fatty-acid imides; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
  • Other known friction modifiers comprise oil-soluble metalic compounds such as organo-molybdenum compounds, organo-titanium compounds and organo-tungsten compounds. Such organo-metallic friction modifiers may also provide antioxidant and antiwear credits to a lubricating oil composition.
  • oil soluble organo-metallic compounds there may be mentioned the carboxylates, dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
  • organo-metallic compounds include molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates, and alkylthioxanthates.
  • Other organo-metallic compounds may include the oil soluble titanium and tungsten carboxylates.
  • oil-soluble or “dispersible” used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • Pour point depressants otherwise known as lube oil flow improvers (LOFI)
  • LOFI lube oil flow improvers
  • Such additives are well known. Typical of those additives that improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polymethacrylates, and maleic anhydride-styrene copolymers esterified with C 8 to C 20 alcohols.
  • Foam control may be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
  • each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function.
  • Representative effective amounts of such additives, when used in crankcase lubricants, are listed below. All the values listed are stated as mass percent active ingredient.
  • additives in the form of 10 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
  • these concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils.
  • the purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
  • the grafted olefin copolymer would usually be employed in the form of a 5 to 15 wt. % concentrate, for example, in a lubricating oil fraction.
  • the amount of concentrate in a finished lubricating oil is from about 0.05 weight percent to about 15 weight percent of the total lubricating oil.
  • the grafted olefin copolymers of the present disclosure will generally be used in admixture with a lube oil base stock, comprising an oil of lubricating viscosity, including natural lubricating oils, synthetic lubricating oils and mixtures thereof.
  • the base oil used which may be used as described herein may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • Such base oil groups are as follows: Table 2 Base Oil Group 1 Sulfur (wt%) Saturates (wt%) Viscosity Index Group I > 0.03 And/or ⁇ 90 80 to 120 Group II ⁇ 0.03 And ⁇ 90 80 to 120 Group III ⁇ 0.03 And ⁇ 90 ⁇ 120 Group IV all polyalphaolefins (PAOs) Group V all others not included in Groups I-IV 1 Groups I-III are mineral oil base stocks.
  • PAOs polyalphaolefins
  • the base oil may also contain a minor or major amount of a poly-alpha-olefin (PAO).
  • PAO poly-alpha-olefin
  • the poly-alpha-olefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms.
  • PAOs include those derived from octene, decene, mixtures thereof, and the like.
  • PAOs may have a viscosity of from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 cSt at 100° C.
  • PAOs examples include 4 cSt at 100° C poly-alpha-olefins, 6 cSt at 100° C poly-alpha-olefins, and mixtures thereof. Mixtures of mineral oil with the foregoing poly-alpha-olefins may be used.
  • the base oil may be an oil derived from Fischer-Tropsch synthesized hydrocarbons.
  • Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.
  • Such hydrocarbons typically require further processing in order to be useful as the base oil.
  • the hydrocarbons may be hydroisomerized using processes disclosed in U.S. Pat. Nos. 6,103,099 or 6,180,575 ; hydrocracked and hydroisomerized using processes disclosed in U.S. Pat. Nos. 4,943,672 or 6,096,940 ; dewaxed using processes disclosed in U.S. Pat. No. 5,882,505 ; or hydroisomerized and dewaxed using processes disclosed in U.S. Pat. Nos. 6,013,171 ; 6,080,301 ; or 6,165,949 .
  • Unrefined, refined, and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove may be used in the base oils.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.
  • the base oil may be combined with an additive composition as disclosed in embodiments herein to provide a crankcase lubricant composition. Accordingly, the base oil may be present in the crankcase lubricant composition in an amount ranging from about 50 wt% to about 95 wt % based on a total weight of the lubricant composition.
  • grafted olefin copolymers have been observed to provide improved high and low temperature properties in lubricant formulations.
  • These properties include kinematic viscosity (KV), cold crank simulator (CCS) viscosity, mini-rotary viscometer viscosity (MRV-TP1), High Temperature High Shear Viscosity, Shear Stability Index, and Temperature Cycled Gelation (TCG).
  • KV Kinematic viscosity
  • CCS Cold Cranking Simulator
  • MRV-TP1 may be measured as described in ASTM D4684.
  • High Temperature High Shear (HTHS) Viscosity may be measured as described in ASTM D4683/D5481.
  • Shear Stability Index may be measured as described in ASTM D6278.
  • Temperature Cycled Gelation (TCG) may be measured by placing the oil in a temperature cycling chamber, where temperature is varied from high to low temperature over a time period. Oil is observed at the low temperature condition; if no gels are observed it passes the test; if gels are observed, it fails the test.
  • the HTHS viscosity of lubricant compositions containing the grafted copolymers described herein may provide an indication of the fuel economy performance of the lubricant composition.
  • polymers experience what is termed as temporary shear by elongating in the shear field.
  • stearic hinderance may prevent the polymers from uncoiling and aligning with the shear field in the engine.
  • Polymers having such stearic hinderance may cause the oil to form a thicker oil film at the boundary of the engine surfaces; a thicker oil film is known to take up more energy in movement which may lead to lower fuel economy.
  • Fluids with relatively low HTHS viscosity provide a lower film thickness and thus may provide better fuel economy.
  • Comparative sample A was a 60 mole % ethylene-propylene non-grafted copolymer that was dissolved in a Group II 110N oil at 7.7 wt%.
  • Comparative sample B was a 80 mole% ethylene-propylene non-grafted copolymer that was dissolved in a Group II 110N oil at 6.5 wt.%.
  • Comparative sample C was the same base polymer used in the preparation of Invention Examples 1-10. Sample C was processed through the extruder under the same conditions as examples 1-10, but no monomers or catalyst were added to this sample. Comparative sample C was dissolved in a Group II 110N oil at 6 wt%.
  • the polymer solutions of the samples of Table 3 and the three comparative polymers solutions were used to formulate SAE 5W-30 oils.
  • the oils contained 10% of a dispersant inhibitor package, 0.2-0.3% of a pour point depressant.
  • the polymer solution was adjusted to a treat rate to obtain a kinematic viscosity of about 10.9 cSt, and the remainder was a mixture of Motiva Star 5 and Star 6 oils in a 87.71/12.29 ratio.
  • the oils were evaluated for Kinematic Viscosity at 100° C, CCS at -30° C, MRV-TP-1 at -35° C, High Temperature High Shear (HTHS) at 150° C and the Temperature Cycled Gelation (TCG) test.
  • HTHS High Temperature High Shear
  • the result of the evaluations of the samples A, B, C and 1-10 are shown in Table 5.
  • the active polymer required to formulate the oils at equal viscosity was much lower for the polymers according to the disclosure (Samples 1-10).
  • the CCS viscosities of Samples (1-10) were 466-1024 cP better than the comparative sample A.
  • the MRV viscosities of the Samples 1-10 were also much improved over the comparative sample A.
  • the HTHS of the Samples 1-10 showed a reduction over the HTHS of all comparative samples, indicating an improvement in fuel economy of an engine operating with these oils.
  • the polymer solutions of samples of Table 3 and the three comparative polymers solutions were used to formulate SAE 10W-40 oils.
  • the oils contained 10% of a dispersant inhibitor package, 0.2-0.5% of a pour point depressant.
  • the polymer solution were adjusted to a treat rate to obtain a kinematic viscosity of about 15.5 cSt, and the remainder was a mixture of Motiva Star 4 and Star 6 oils in a 28.44/710.56 ratio.
  • the oils were evaluated for Kinematic Viscosity at 100° C, CCS at -25° C, MRV-TP-1 at -30° C, High Temperature High Shear (HTHS) at 150° C and the Temperature Cycled Gelation (TCG) test. The results of these evaluations are shown in Table 6.
  • the active polymer required to formulate the oils at equal viscosity was much lower for the polymers of Samples 1-10 than for Samples A, B, and C.
  • the CCS viscosities of Samples 1-10 were 400-795 cP better than for comparative sample A.
  • the MRV viscosities of the Samples 1-10 was also much improved over comparative sample A.
  • the HTHS of the Samples 1-10 showed a significant reduction over the HTHS of all the comparative samples A, B, and C, indicating an improvement in fuel economy of an engine operating with the oils of Samples 1-10.
  • the temperature cycled gelation of the Samples 1-10 was improved over the comparative sample B and C, both of which were 80 mole % ethylene-propylene copolymers, and were known to be crystalline materials prone to gelation.
  • the polymers of Samples 1-10 lowered the treat rate, improved CCS, MRV, HTHS and TCG performance of the SAE 5W-30 oils.
  • TCG temperature cycled gelation
  • lubricating oils containing higher levels of active polymer may require more graft monomers, longer chain graft monomers and higher catalyst levels.
  • lighter oils such as 5W30 oils (Table 4, sample 3-8), where the levels of the active polymer were lower (about 0.5 wt.%), a minimum of 15 wt.% alpha-olefin of C10 or higher chain length was required to pass the TCG test.
  • 15 wt.% or higher of a C10 alpha olefin is sufficient, but higher catalyst levels were required to pass the TCG test.
  • wax content of base oils may also have an effect on the monomer level, chain length of monomer, and catalyst level necessary to pass the TCG test. This is because more waxy base oils may have a greater propensity for interaction with polymer chains. Therefore, the skilled person may use an appropriate graft monomer, level and catalyst level to counteract such interaction and pass the TCG tests.
  • the grafted polymers of Samples 11-14 were dissolved in a Group II 110 N base oil at 8 wt% polymer in the base oil.
  • the viscosities at 100° C of these polymer solutions were measured by ASTM D445.
  • the molecular weight of the samples was measured by gel permeation technology using polystyrene standards. These results are shown in Table 8.
  • the polymer solutions of the samples of Table 8 and the ungrafted comparative base polymer solutions were used to formulate SAE 5W-30 oils.
  • the oils contained 10% of a dispersant inhibitor package, 0.2-0.3% of a pour point depressant.
  • the polymer solution was adjusted to a treat rate to obtain a kinematic viscosity of about 10.9 cSt, and the remainder was a mixture of Motiva Star 5 and Star 6 oils in a 87.71/12.29 ratio.
  • the oils were evaluated for Kinematic Viscosity at 100° C, CCS at -30° C, MRV-TP-1 at -35° C, High Temperature High Shear (HTHS) at 150° C and the Temperature Cycled Gelation (TCG) test. The results of these evaluations are shown in Table 9.
  • the active polymer required to formulate the oils at equal viscosity was much lower for the polymers of Samples 11-14 than for the base polymer.
  • the HTHS of Samples 11-14 showed significant reduction over the HTHS of all comparative samples, indicating an improvement in fuel economy of an engine operating with these oils.
  • the polymers of Samples 11-14 lowered the treat rate and HTHS performance of the SAE 5W-30 oils. From the results of Samples 1-14, it was demonstrated that the polymers according to the disclosure were capable of producing engine oils with low HTHS, and improved fuel economy, regardless of the ethylene content of the polymer backbone.
  • the SAE J300 standard specifies a 2.90 cP minimum HTHS for 5W30 oils. It is recognized that the oils made with the polymer of Samples 11-14 have a HTHS lower than this minimum.
  • a mixture of grafted and ungrafted polymers may be used. For example, a 75/25 mixture of the polymer of Sample 11 and Sample A may be used to produce a 5W-30 oil with a HTHS of 2.9 cP.
  • the grafted copolymers of the disclosure may provide better CCS viscosities and MRV at lower pour point treatment rates and may also improve fuel economy as indicated by the HTHS viscosities of the lubricant compositions containing the grafted copolymers.
  • compositions described as "comprising" a plurality of defined components are to be construed as including compositions formed by admixing the defined plurality of defined components.
  • the principles, preferred embodiments and modes of operation of the present disclosure have been described in the foregoing specification. What applicants submit, however, is not to be construed as limited to the particular embodiments disclosed, since the disclosed embodiments are regarded as illustrative rather than limiting.

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EP10188282A 2009-11-05 2010-10-20 Olefin Copolymer VI improvers and lubricant compositions and uses thereof Active EP2325291B1 (en)

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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9127151B2 (en) 2009-04-28 2015-09-08 Exxonmobil Chemical Patents Inc. Polymer compositions having improved properties as viscosity index improvers and use thereof in lubricating oils
JP5638256B2 (ja) * 2010-02-09 2014-12-10 出光興産株式会社 潤滑油組成物
FR2980799B1 (fr) 2011-09-29 2013-10-04 Total Raffinage Marketing Composition lubrifiante pour moteur marin
CN109135034A (zh) * 2012-02-03 2019-01-04 埃克森美孚化学专利公司 可用于油料改性剂的聚合物组合物的制备方法
FR3011246A1 (fr) * 2013-09-27 2015-04-03 Total Marketing Services Composition lubrifiante a base de copolymeres ethylene/propylene
CN104194868A (zh) * 2014-09-16 2014-12-10 吉林化工学院 一种耐低温型粘度指数改进剂及其制备方法
US10550349B2 (en) * 2015-07-16 2020-02-04 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
US11155764B2 (en) 2016-05-05 2021-10-26 Afton Chemical Corporation Lubricants for use in boosted engines
CN109504495B (zh) * 2019-01-25 2022-02-01 中沃能源(湖北)集团有限公司 一种润滑油用改进剂及其制备工艺
CN110499206B (zh) * 2019-08-14 2020-10-16 深圳昆油石化技术有限公司 含有星型sep共聚物润滑油粘度指数改性剂及其制备方法
US11680222B2 (en) * 2020-10-30 2023-06-20 Afton Chemical Corporation Engine oils with low temperature pumpability

Family Cites Families (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
US3366569A (en) 1959-03-30 1968-01-30 Lubrizol Corp Lubricating compositions containing the reaction product of a substituted succinic acid-producing compound, an amino compound, and an alkenyl cyanide
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3185704A (en) 1962-09-04 1965-05-25 Exxon Research Engineering Co Formamide of mono-alkenyl succinimide
US3509055A (en) 1962-09-04 1970-04-28 Rohm & Haas Oil-soluble dispersants,methods of making them and lubricating compositions containing them
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
NL137371C (zh) 1963-08-02
GB1053340A (zh) 1963-10-14 1900-01-01
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3442808A (en) 1966-11-01 1969-05-06 Standard Oil Co Lubricating oil additives
US3862265A (en) 1971-04-09 1975-01-21 Exxon Research Engineering Co Polymers with improved properties and process therefor
US3912764A (en) 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
DE2437787C3 (de) * 1974-08-06 1978-10-05 Basf Ag, 6700 Ludwigshafen Mineralschmieröle
FR2293485A1 (fr) 1974-12-03 1976-07-02 Inst Francais Du Petrole Compositions lubrifiantes ameliorees par l'addition de copolymeres greffes
US4026809A (en) 1974-12-19 1977-05-31 Texaco Inc. Lubricating compositions containing methacrylate ester graft copolymers as useful viscosity index improvers
CA1088694A (en) 1975-07-31 1980-10-28 Robert L. Stambaugh Polyolefin grafted with polymers of nitrogen containing monomers and lubricants and fuel compositions containing same
US4110349A (en) 1976-06-11 1978-08-29 The Lubrizol Corporation Two-step method for the alkenylation of maleic anhydride and related compounds
DE2702604C2 (de) 1977-01-22 1984-08-30 Basf Ag, 6700 Ludwigshafen Polyisobutene
US4161452A (en) * 1977-01-28 1979-07-17 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4160739A (en) 1977-12-05 1979-07-10 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4388202A (en) 1978-11-14 1983-06-14 Mitsui Petrochemical Industries, Ltd. Lubricating oil composition and process for preparation thereof
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
US4686054A (en) 1981-08-17 1987-08-11 Exxon Research & Engineering Co. Succinimide lubricating oil dispersant
DE3207291A1 (de) 1982-03-01 1983-09-08 Röhm GmbH, 6100 Darmstadt Konzentrierte emulsionen von olefincopolymerisaten
US4476283A (en) * 1982-11-12 1984-10-09 Uniroyal, Inc. Graft copolymerization process
US4661549A (en) 1983-10-12 1987-04-28 Occidental Chemical Corporation Graft polymers of polymerizable monomers and olefin polymers
US4579675A (en) 1983-11-09 1986-04-01 Texaco Inc. N-substituted enaminones and oleaginous compositions containing same
US4612132A (en) 1984-07-20 1986-09-16 Chevron Research Company Modified succinimides
CA1261499A (en) 1984-11-22 1989-09-26 Tatsuo Kinoshita Modified ethylenic random copolymer
US4611031A (en) 1985-01-28 1986-09-09 Rohm And Haas Company Process for the preparation of a compatibilizer for concentrated polymer blends and compatibilizer product
US4636322A (en) 1985-11-04 1987-01-13 Texaco Inc. Lubricating oil dispersant and viton seal additives
US4663064A (en) 1986-03-28 1987-05-05 Texaco Inc. Dibaisic acid lubricating oil dispersant and viton seal additives
US4826613A (en) 1986-09-22 1989-05-02 Texaco Inc. Lubricating oil containing dispersant viscosity index improver
US4839072A (en) 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts
US4839071A (en) 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in lubricating oil compositions
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
CA1338288C (en) 1989-02-07 1996-04-30 Jai Gopal Bansal Method for the production of long chain hydrocarbyl substituted mono- or dicarboxylic acid materials
CA1335895C (en) 1989-02-07 1995-06-13 Exxon Chemical Patents Inc. Low temperature method for the production of long chain hydrocarbyl substituted mono- or dicarboxylic acid materials employing plural zone mixing
US5140074A (en) 1990-01-26 1992-08-18 Himont Incorporated Method of producing olefin polymer graft copolymers
US5075383A (en) 1990-04-11 1991-12-24 Texaco Inc. Dispersant and antioxidant additive and lubricating oil composition containing same
US5397842A (en) * 1991-08-20 1995-03-14 Rohm And Haas Company Polyolefin/segmented copolymer blend and process
US5334321A (en) 1993-03-09 1994-08-02 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Modified high molecular weight succinimides
US5356552A (en) 1993-03-09 1994-10-18 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free lubricating oils having modified high molecular weight succinimides
JP2684314B2 (ja) 1993-06-04 1997-12-03 三洋化成工業株式会社 重合体組成物および潤滑油組成物
US5837773A (en) 1993-08-02 1998-11-17 Dsm Copolymer, Inc. Sheared polymer blends and process for their preparation
US5663126A (en) 1994-10-21 1997-09-02 Castrol Limited Polar grafted polyolefins, methods for their manufacture, and lubricating oil compositions containing them
US5821205A (en) 1995-12-01 1998-10-13 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5716912A (en) 1996-04-09 1998-02-10 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
BR9611898A (pt) 1995-12-08 2000-05-16 Exxon Research Engineering Co Processo para a produção de um óleo de base de hidrocarboneto biodegradável de alto desempenho, e, respectivo óleo
US5777025A (en) 1996-02-09 1998-07-07 Exxon Chemical Patents Inc. Process for preparing polyalkenyl substituted C4 to C10 dicarboxylic acid producing materials
US5891953A (en) 1996-02-09 1999-04-06 Exxon Chemical Patents Inc Process for preparing polyalkenyl substituted mono- and dicarboxylic acid producing materials (PT-1302)
GB9611318D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611424D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611316D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611428D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US5882505A (en) 1997-06-03 1999-03-16 Exxon Research And Engineering Company Conversion of fisher-tropsch waxes to lubricants by countercurrent processing
US6110880A (en) 1997-06-24 2000-08-29 Exxon Chemical Patents Inc Polyolefin block copolymer viscosity modifier
US5861363A (en) 1998-01-29 1999-01-19 Chevron Chemical Company Llc Polyalkylene succinimide composition useful in internal combustion engines
US6107257A (en) * 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6013171A (en) 1998-02-03 2000-01-11 Exxon Research And Engineering Co. Catalytic dewaxing with trivalent rare earth metal ion exchanged ferrierite
US6180575B1 (en) 1998-08-04 2001-01-30 Mobil Oil Corporation High performance lubricating oils
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6103099A (en) 1998-09-04 2000-08-15 Exxon Research And Engineering Company Production of synthetic lubricant and lubricant base stock without dewaxing
ATE298780T1 (de) 1998-12-09 2005-07-15 Mitsui Chemicals Inc Vikositätsveränderer für schmieröle und schmierölzusammensetzung
CN1179025C (zh) * 1998-12-10 2004-12-08 乙基公司 高度接枝的多功能烯烃共聚物粘度指数改进剂
WO2001085880A1 (fr) 2000-05-10 2001-11-15 Mitsui Chemicals, Inc. Modificateur de viscosite pour huile lubrifiante et composition d'huile lubrifiante
US20030216509A1 (en) * 2000-05-26 2003-11-20 Gabriele Goethel Substantially random interpolymer grafted witn one or more olefinically unsaturated organic monomers
WO2002010276A2 (en) * 2000-07-31 2002-02-07 The Lubrizol Corporation Polymeric mixture useful as viscosity improver for lubricating oils
JP2004143436A (ja) * 2002-10-02 2004-05-20 Idemitsu Petrochem Co Ltd オレフィン系グラフト共重合体の製造方法
US7429555B2 (en) 2004-04-30 2008-09-30 Rohmax Additives Gmbh Lubricating grease with high water resistance
JP4485269B2 (ja) 2004-06-25 2010-06-16 三井化学株式会社 新規グラフト共重合体
JP4485268B2 (ja) 2004-06-25 2010-06-16 三井化学株式会社 ポリオレフィンマクロモノマーおよびその製造方法
JPWO2006028169A1 (ja) 2004-09-10 2008-05-08 三井化学株式会社 潤滑油用粘度調整剤、潤滑油用添加剤組成物および潤滑油組成物
US20070191242A1 (en) * 2004-09-17 2007-08-16 Sanjay Srinivasan Viscosity modifiers for lubricant compositions
US7253231B2 (en) 2005-01-31 2007-08-07 Afton Chemical Corporation Grafted multi-functional olefin copolymer VI modifiers and uses thereof
ATE510903T1 (de) * 2005-05-20 2011-06-15 Infineum Int Ltd Verwendung von schmierölzusammensetzungen zur verschleissreduzierung von mit drehendem zapfer versehenen personenkraftwagenmotoren
FR2892885B1 (fr) * 2005-11-02 2008-01-25 Streamezzo Sa Procede de gestion de polices de caractere a l'interieur de scenes multimedia, programme d'ordinateur et terminal correspondants.
US8580719B2 (en) 2006-03-31 2013-11-12 Idemitsu Kosan Co., Ltd. Lubricating oil composition for internal combustion engine
US8293689B2 (en) 2006-05-08 2012-10-23 The Lubrizol Corporation Lubricating composition containing a polymer and antiwear agents
US7696138B2 (en) * 2006-07-28 2010-04-13 Afton Chemical Corporation Alkyl acrylate copolymer dispersants and uses thereof
US8420583B2 (en) * 2008-01-24 2013-04-16 Afton Chemical Corporation Olefin copolymer dispersant VI improver and lubricant compositions and uses thereof

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SG170669A1 (en) 2011-05-30
CN102051251A (zh) 2011-05-11
US8415284B2 (en) 2013-04-09
US20110105371A1 (en) 2011-05-05
JP2011099093A (ja) 2011-05-19
JP5635350B2 (ja) 2014-12-03
EP2325291A1 (en) 2011-05-25
CN102051251B (zh) 2013-08-21

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